WO2004079027A1 - Duplex stainless steel alloy for use in seawater applications - Google Patents
Duplex stainless steel alloy for use in seawater applications Download PDFInfo
- Publication number
- WO2004079027A1 WO2004079027A1 PCT/SE2004/000223 SE2004000223W WO2004079027A1 WO 2004079027 A1 WO2004079027 A1 WO 2004079027A1 SE 2004000223 W SE2004000223 W SE 2004000223W WO 2004079027 A1 WO2004079027 A1 WO 2004079027A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- content
- alloy
- alloy according
- max
- Prior art date
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 68
- 239000000956 alloy Substances 0.000 title claims abstract description 68
- 229910001039 duplex stainless steel Inorganic materials 0.000 title claims abstract description 11
- 239000013535 sea water Substances 0.000 title claims description 6
- 239000000463 material Substances 0.000 claims abstract description 46
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 230000008878 coupling Effects 0.000 claims abstract description 7
- 238000010168 coupling process Methods 0.000 claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 238000010276 construction Methods 0.000 claims abstract description 5
- 238000011109 contamination Methods 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims description 37
- 229910052804 chromium Inorganic materials 0.000 claims description 26
- 229910001566 austenite Inorganic materials 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 210000003954 umbilical cord Anatomy 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 60
- 230000007797 corrosion Effects 0.000 abstract description 60
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 2
- 229910001256 stainless steel alloy Inorganic materials 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 23
- 229910000831 Steel Inorganic materials 0.000 description 18
- 239000010959 steel Substances 0.000 description 18
- 238000005275 alloying Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000011835 investigation Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 9
- 229910001114 SAF 2507 Inorganic materials 0.000 description 7
- 102220043852 rs72857097 Human genes 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000033001 locomotion Effects 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- -1 chromium carbides Chemical class 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- VCTOKJRTAUILIH-UHFFFAOYSA-N manganese(2+);sulfide Chemical class [S-2].[Mn+2] VCTOKJRTAUILIH-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
Definitions
- the present invention relates to a stainless steel alloy, more precisely a duplex stainless steel alloy having ferritic-austenitic matrix and having high corrosion resistance in combination with good structural stability and hot workability, in particular a duplex stainless steel having a ferrite content of 40-65 % by volume and a well-balanced composition that gives the material corrosion properties making it more suit- able for use in chloride-containing environments than what has previously been found possible.
- Valves and couplings on the unit at the bottom of the sea are controlled hydraulically and electrically from a platform, a production ship or another unit on the surface of the sea or on land.
- An umbilical cord pipe a so-called umbilical, couples together the guiding unit with the units on the bottom of the sea.
- the part of the umbilical that lies on the bottom of the sea, for instance, between two underwater units on different extraction sites, is called static umbilical since the same only to a relatively small extent is effected by the motions of the sea.
- the part of the umbilical, that is situated between the bottom of the sea and the surface is called dynamic umbilical and is effected to a large extent by motions in the water and on the surface. Examples of such motions are flows in the water, wave motions as well as motions of the platform and the production ship.
- the demands that are made on the pipes in an umbilical are foremost related to corrosion and mechanical properties.
- the pipe material has to be resistant to corrosion in sea water, which surrounds the outer surface of the pipes. This property is what is regarded as being most important, since sea water has a very corrosive impact on stainless steel. Furthermore, the material has to have high corrosion resistance to the possible corrosive solutions that are injected in the oil well. The material has to be compatible with hydraulic liquids without contaminating the liquid. Possible contamination may affect the service function of the control unit at the bottom of the sea very
- the mechanical properties of the used pipe material are very important for the application of umbilical pipes. Since the depth may be considerable on the site of the oil production, the dynamic part of the umbilical generally becomes long, and thereby heavy. The weight has to be carried by the platform or the floating production ship. In practice, there is two ways to decrease the weight of an umbilical having a given configuration. It is possible to choose a lighter material or a material having the same density but having higher tensile yield limit and ultimate tensile strength. By choosing a material having higher strength, pipes having thinner wall may be used, and thereby the total mass of the umbilical is reduced. The deeper the sea at the site of extraction, the more important the total weight per unit of length of umbilical of the material will be.
- Duplex steel alloys that were established as an alternative to hitherto used types of steel, such as, for instance, ferritic steel that previously were used in this application, nickel base alloys or other high-alloy steels, are not excepted from this development.
- PRE Pitting Resistance Equivalent
- the principal alloying elements that affect this property are, according to the formula, Cr, Mo, N.
- An example of such a steel grade is seen in EP 0 220 141 , which through this reference hereby is included in this description.
- This steel grade, having the trade mark of SAF 2507 (UNS S32750), has essentially been alloyed with high contents of Cr, Mo and N. Thus, it is developed towards this property with, above all, good corrosion resistance in chloride environments.
- the elements Cu and W have turned out to be efficient alloying additives for additional optimization of the corrosion properties of the steel in chloride environments.
- the element W has, on that occasion, been used as substitution for a part of Mo, as for instance in the commercial alloys DP3W (UNS S39274) or ZeronlOO, which contain 2,0 % and 0,7 % of W, respectively.
- the latter also contains 0,7 % of Cu with the purpose of increasing the alloy's corrosion resistance in acid environments.
- PREW % Cr + 3,3(% Mo + 0,5 % W) + 16 % N, as described, for instance, in EP 0 545 753, which relates to a duplex stainless alloy having generally improved corrosion properties.
- the above-described steel grades have a PRE number, irrespective of method of calculation, which is above 40 but the PRE number is limited upwards to about 43 since higher values mean that the alloys obtain inferior structural stability.
- a higher degree of alloying increases the risk of precipitation of intermetallic phase, and therefore the level of alloying in duplex steel is regarded as limited to achieve PRE values around a maximum of about 43, irrespective of method of calculation.
- SAF 2906 should also be mentioned, the composition of which is seen in EP 0 708 845.
- This alloy which is characterized by higher contents of Cr and N in comparison with, for instance, SAF 2507, has turned out to be especially suitable for use in environments 5 where the resistance to intercrystalline corrosion and corrosion in ammonium carba- mate is of importance, but it has also a high corrosion resistance in chloride-containing environments.
- the alloy has a corrosion resistance in chloride environment corresponding to the o alloy UNS S32750, but simultaneously a higher yield point in tension Rpo,2- This makes that this alloy has advantages in comparison with UNS S32750 as umbilical material, since lower weight of the umbilical can be obtained.
- the corrosion resistance gives, however, no improvements in comparison with UNS S32750, which means considerable limitations in umbilical pipes that are exposed to higher tem- 5 peratures in future plants.
- the alloy 19D (UNS S32001 ) is a duplex alloy characterized by the composition 19,5-21 ,5 % of Cr, 0,05-0,17 % of N and max 0,6 % of Mo.
- This alloy has a PRE number of about 22, and therefore the alloy is unsuitable in sea-water applications o such as umbilicals. Accordingly, in order to achieve a sufficient corrosion resistance in this alloy, a cathode protection has to be applied in the form of a zinc layer on the outer surface of the umbilical pipe. If the zinc layer is consumed or if a greater surface becomes damaged, the corrosion protection is, however, ruined and a fast corrosion process may occur, which means expensive repairs and down periods. 5
- austenitic steels with PRE numbers of up to 55 having been made possible by the addition of high contents of Cr, Mo and N combined with high contents of Ni.
- Said alloys should work 5 very well to the new tougher corrosion conditions in umbilicals.
- the disadvantage of the same alloys is that they have considerably lower yield point in tension than duplex steel and are, furthermore, considerably more expensive to manufacture, foremost by virtue of their high percentage of Ni, which is an expensive alloying material.
- austenites having good resistance in chloride environment are UNS S32654 having a PRE number of about 55, and UNS S34565 having a PRE number of about 45. These have, however, too low a strength and high a cost in order to be a realistic alternative for umbilical pipes.
- the pitting resistance of duplex stainless steel an increase of the PRE number is required in both the ferrite phase and the austenite phase without, because of this, jeopardizing the structural stability or the workability of the material. If the composition in the two phases is not equivalent in respect of the active alloying components, one of the phases becomes more susceptible to pitting and crevice corrosion. Thus, the more corrosion-susceptible phase controls the resistance of the alloy, while the structural stability is controlled by the highest alloyed phase.
- CPT Critical Pitting Corrosion Temperature
- CCT Critical Crevice Corrosion Temperature
- the material according to the present invention has, in view of the high alloy content thereof, extraordinarily good workability, in particular hot-workability, and should thereby be very suitable to be used for, for instance, the manufacture of bars, pipes, such as welded and seamless pipes, weld material, construction parts such as, for instance, flanges and couplings.
- duplex stain- less steel alloys which contain (in % by weight)
- FIG 1 shows CPT values from test of the experimental charges in the modified
- the alloy according to the invention contains (in % by weight):
- Carbon (C) has limited solubility in both ferrite and austenite.
- the limited solubility means a risk of precipitation of chromium carbides and therefore the content should not exceed 0,03 % by weight, preferably not exceed 0,02 % by weight.
- Si Silicon
- Si is utilized as deoxidizer in the steel production and increases the flowabil- ity in production and upon welding.
- too high contents of Si lead to precipi- tation of undesired intermetallic phase, and therefore the content should be limited to max 0,5 % by weight, preferably max 0,3 % by weight.
- Manganese (Mn) is added in order to increase the solubility of N in the material.
- Mn only has a limited impact on the solubility of N in the alloy type in question. Instead, there are other elements having higher impact on the solubility.
- Mn may in combination with high sulphur contents give rise to the formation of manganese sulphides, which work as initiation spots for pitting. Therefore, the content of Mn should be limited to between 0-3,0 % by weight, preferably 0,5-1 ,2 % by weight.
- Chromium (Cr) is a very active element in order to improve the resistance to the majority of corrosion types. Furthermore, a high chromium content means that a very good solubility of N is obtained in the material. Thus, it is desirable to hold the content of Cr as high as possible in order to improve the corrosion resistance. For very good values of the corrosion resistance, the chromium content should be at least
- Nickel (Ni) is used as austenite-stabilizing element and is added in suitable contents so that the desired ferrite content is attained.
- an addition of between 4,9-10,0 % by weight of nickel is required, preferably 4,9-9,0 % by weight, in particular 6,0-9,0 % by weight.
- Molybdenum (Mo) is an active element that improves the corrosion resistance in chloride environments as well as preferably in reducing acids. Too high a content of Mo, in combination with the contents of Cr being high, means that the risk of inter- metallic precipitations increases.
- the content of Mo in the present invention should be in the interval of 3,0-5,0 % by weight, preferably 3,6-4,9 % by weight, in particular 4 ,4-4,9 % by weight.
- N Nitrogen
- N is a very active element that increases the corrosion resistance, the structural stability as well as the strength of the material. Furthermore, a high content of N improves the reformation of austenite after welding, which gives good properties of welded joints. In order to achieve a good effect from N, at least 0,28 % by weight of N should be added. At high contents of N, the risk of precipitation of chromium nitrides increases, especially when the chromium content simultaneously is high. Furthermore, a high content of N means that the risk of porosity increases by virtue of the solubility of N in the charge being exceeded. The content of N should, for these reasons, be limited to max 0,5 % by weight, preferably is >0, 35-0,45 % by weight of N added.
- Boron (B) is added in order to increase the hot workability of the material. At too high a boron content, the weldability and the corrosion resistance may be deteriorated.
- the boron content should be greater than 0 and up to 0,0030 % by weight.
- S Sulphur
- S Sulphur
- Co Co
- Co is added foremost in order to improve the structural stability as well as the corrosion resistance.
- Co is an austenite stabilizer.
- at least 0,5 % by weight preferably at least 1 ,0 % by weight should be added. Since cobalt is a relatively expensive element, the cobalt addition is therefore limited to max 3,5 % by weight.
- Tungsten increases the resistance to pitting and crevice corrosion. But addition of too high contents of tungsten in combination with the contents of Cr and contents of Mo being high, means that the risk of intermetallic precipitations increases.
- the content of W in the present invention should be in the interval of 0-3,0 % by weight, preferably between 0-1 ,8 % by weight.
- Copper is added in order to improve the corrosion resistance in acid environments such as sulphuric acid. Cu also affects the structural stability. However, high contents of Cu means that the solid solubility is exceeded. Therefore, the content of Cu is limited to max 2,0 % by weight, preferably between 0,1 and 1 ,5 % by weight.
- Ruthenium (Ru) is added in order to increase the corros on resistance. Ruthenium is a very expensive element, and therefore the content is I mited to max 0,3 % by weight, preferably greater than 0 and up to 0,1 % by we ght.
- Al aluminium
- Ca Calcium
- the ferrite content is important in order to obtain good mechanical properties and corrosion properties as well as good weldability. From a corrosion and a weldability point of view, it is desirable having a ferrite content of between 40-65 % in order to obtain good properties. Furthermore, high ferrite contents means that the low-temperature impact resistance as well as the resistance to hydrogen embrittlement risk being deteriorated. Therefore, the ferrite content is 40-65 % by volume, preferably
- Experimental charges according to this example were produced by laboratory casting of 170 kg of ingot that was hot-forged into round bar. The same was hot extruded into bar (round bar as well as flat bar), where test material was sampled from round bar. Furthermore, flat bar was annealed before cold rolling took place, and then additional test material was sampled. The process may, from a material technology point of view, be regarded as representative for the manufacture on a larger scale, for instance for the manufacture of seamless pipes by means of the extrusion method followed by cold rolling. Table 2 shows composition of experimental charges of the first batch.
- Tmax sigma is calculated by means of Thermo-Calc (T-C version N the thermody- namic database of steel TCFE99) based on guiding values of all stated elements in the different variants.
- T max sigma is the resolution temperature of the sigma phase, with high resolution temperature indicating lower structural stability. Table 3
- the object of this investigation is to be able to rank materials in respect of the structural stability, i.e. this is not the actual content of sigma phase in the test pieces that have been heat treated and quenched before, for instance, corrosion test. It is evident that T max sigma that has been calculated by means of Thermo-calc does not directly corresponds with measured quantity of sigma phase, but in this investigation it is, however, clear that the experimental charges having the lowest calculated T max sigma contain the lowest quantity of sigma phase.
- the pitting properties of all charges have been tested for ranking in the so-called "Green Death” solution that consists of 1 % FeCI 3 , 1 % CuCI 2) 11 % H 2 S0 4 , 12 % HCI .
- the test procedure corresponds to the pitting testing according to ASTM G48C, but is carried out in the more aggressive "Green Death” solution. Furthermore, some charges have been tested according to ASTM G48C (2 experiments per charge). Also electrochemical testing in 3 % NaCI (6 experiments per charge) has been carried out.
- the results in the form of critical pitting temperature (CPT) from all experiments are seen in Table 4, such as the PREW number (Cr + 3,3(Mo + 0,5 W) + 16 N) of the total alloy composition as well as of austenite and ferrite.
- the indexing alpha relates to ferrite and gamma relates to austenite.
- Test charge 605 183 alloyed with cobalt shows good structural stability at controlled cooling rate (-140 °C/min), in spite of it containing high contents of chromium as well as molybdenum, has better results than SAF 2507 as well as SAF 2906.
- Table 7 shows results from Tungsten Inert Gas remelting test (henceforth abbreviated TIG), with the charges 605 193, 605 183, 605 184 as well as 605 253 having a stable structure in the heat affected zone (henceforth abbreviated HAZ).
- TIG Tungsten Inert Gas remelting test
- HAZ heat affected zone
- Example 2 In the example below, the composition is given of an additional number of experimental charges manufactured with the intention of finding the optimal composition. Said charges are modified, based on the properties of the charges having good structural stability as well as high corrosion resistance, from the results that were shown in Example 1. All charges in Table 8 are comprised of the composition according to the present invention, with charges 1-8 being included in a statistical experimental plan, while charges e to n are additional experimental alloys within the scope of this invention.
- the pitting properties of all charges have been tested in the "Green Death” solution (1 % FeCI 3 , 1 % CuCI 2 , 11 % H 2 S0 4 , 1 ,2 % HCI) for ranking.
- the test procedure is the same as pitting testing according to ASTM G48C, but the testing is carried out in a more aggressive solution than 6 % FeC , the so-called "Green Death” solution.
- general corrosion test in 2 % HCI (2 experiments per charge) has been carried out for ranking before dew point testing. The results from all experiments are seen in Table 10, Figure 2 and Figure 3. All tested charges perform better than SAF 2507 in the Green Death solution.
- the PREW number (% Cr + 3,3 %(Mo + 0,5 % W) + 16 % N) is given for the total alloy composition and PRE in austenite as well as ferrite (rounded) based on phase composition being measured by means of micro probe.
- the ferrite content is measured after heat treatment at 1100 °C followed by water quenching.
- Structural control shows that the charges 605 249, 605 251 , 605 252, 605253, 605 254, 605 255, 605 259, 605 260, 605 266 as well as 605 267 are free from undesired sigma phase. Furthermore, charge 605 249, alloyed with 1 ,5 % by weight of cobalt, is free from sigma phase, while charge 605 250, alloyed with 0,6 % by weight of cobalt, contains a little sigma phase. 0 Both charges are alloyed with high percentage of chromium, almost 29,0 % by weight, as well as molybdenum content of almost 4,25 % by weight.
- compositions of the charges 605 249, 605 250, 605 251 and 605 252 are compared considering the sigma phase content, it is very clear that the composition interval for the optimal material in respect of, in this case, structural stability, is very narrow. 5 Furthermore, it is evident that charge 605 268 contains only occasional sigma phase in comparison with charge 605 263, which contains much sigma phase. What essentially separates these charges, is addition of copper to charge 605 268. In charge 605 266 as well as 605 267, the sigma phase is free in spite of high chromium content, the later charge is alloyed with copper.
- the charges o 605 262 and 605 263, having the addition of 1 ,0 % by weight of tungsten have a structure with much sigma phase, while it is interesting to note that charge 605 269, also having 1 ,0 % by weight of tungsten but of a higher nitrogen content than 605 262 and 605 263, has a considerably smaller quantity of sigma phase.
- charge 605 269 also having 1 ,0 % by weight of tungsten but of a higher nitrogen content than 605 262 and 605 263, has a considerably smaller quantity of sigma phase.
- a very well-adjusted balance between the various alloying elements is required at 5 these high alloy contents for, e.g. , chromium and molybdenum, in order to obtain good structural properties.
- Table 12 shows the results from the light optical investigation after annealing at 1080 °C, 20 min, followed by water quenching.
- the amount of sigma phase is indi- o cated by means of values from 1 to 5, with 1 representing that no sigma phase has been detected upon the investigation, while 5 representing that a very high percentage of sigma phase has been detected upon the investigation.
- results are shown from impact resistance testing of some of the charges. The results are very good, which indicates a fine structure after annealing at 1100 °C followed by water quenching and the requirement of 100 J is met by a large margin by all tested charges.
- Figure 4 shows the results from hot ductility test of most of the charges.
- a good workability is naturally crucial in order to be able to manufacture the material into product shapes such as bars, pipes, such as welded and seamless pipes, thread, weld material, construction parts such as, for instance, flanges and couplings.
- the strain controlled fatigue properties give information about how much, and how many times, a material may be elongated, before strain controlled fatigue cracks arise in the material. Since umbilical pipes are welded together into long lengths, are reeled on drums before the are twisted into the umbilical, it is not unusual that a number of operations occurs where certain plastic deformation arises before the umbilical starts function.
- the strain controlled fatigue data that has been established emphasize that the risk of rupture as a consequence of strain controlled fatigue in an umbilical pipe borders on zero.
- the strength that is required for being able to substantially reduce the weight of an umbilical is:
- the material according to the present invention has, in view of the high alloy content thereof, extraordinarily good workability, in particular hot-workability, and should thereby be very suitable to be used for, for instance, the manufacture of bars, pipes, such as welded and weldless pipes, weld material, construction parts, such as, for instance, flanges and couplings.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Articles (AREA)
- Arc Welding In General (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002519786A CA2519786A1 (en) | 2003-03-02 | 2004-02-19 | Duplex stainless steel alloy for use in seawater applications |
EP04712794A EP1599612A1 (en) | 2003-03-02 | 2004-02-19 | Duplex stainless steel alloy for use in seawater applications |
US10/547,572 US20070089810A1 (en) | 2003-03-02 | 2004-02-19 | Duplex stainless steel alloy for use in seawater applications |
JP2006507921A JP2006519313A (en) | 2003-03-02 | 2004-02-19 | Duplex stainless steel used in seawater equipment |
EA200501409A EA009108B1 (en) | 2003-03-02 | 2004-02-19 | Duplex stainless steel alloy for use in seawater applications |
AU2004217572A AU2004217572A1 (en) | 2003-03-02 | 2004-02-19 | Duplex stainless steel alloy for use in seawater applications |
NO20054105A NO20054105L (en) | 2003-03-02 | 2005-09-02 | Duplex stainless steel alloy for use in fun applications |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE0300574-1 | 2003-03-02 | ||
SE0300574A SE527178C2 (en) | 2003-03-02 | 2003-03-02 | Use of a duplex stainless steel alloy |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004079027A1 true WO2004079027A1 (en) | 2004-09-16 |
Family
ID=20290561
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/SE2004/000223 WO2004079027A1 (en) | 2003-03-02 | 2004-02-19 | Duplex stainless steel alloy for use in seawater applications |
Country Status (11)
Country | Link |
---|---|
US (1) | US20070089810A1 (en) |
EP (1) | EP1599612A1 (en) |
JP (1) | JP2006519313A (en) |
KR (1) | KR20060056886A (en) |
CN (1) | CN100457953C (en) |
AU (1) | AU2004217572A1 (en) |
CA (1) | CA2519786A1 (en) |
EA (1) | EA009108B1 (en) |
NO (1) | NO20054105L (en) |
SE (1) | SE527178C2 (en) |
WO (1) | WO2004079027A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008054300A1 (en) * | 2006-10-30 | 2008-05-08 | Sandvik Intellectual Property Ab | Duplex stainless steel alloy and use of this alloy |
WO2012161661A1 (en) | 2011-05-26 | 2012-11-29 | United Pipelines Asia Pacific Pte Limited | Austenitic stainless steel |
US9381585B2 (en) | 2010-03-03 | 2016-07-05 | Sandvik Intellectual Property Ab | Method of manufacturing a stainless steel product |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008179844A (en) * | 2007-01-23 | 2008-08-07 | Yamaha Marine Co Ltd | Two-phase stainless steel and casting of two-phase stainless steel |
US8535606B2 (en) * | 2008-07-11 | 2013-09-17 | Baker Hughes Incorporated | Pitting corrosion resistant non-magnetic stainless steel |
CN101704168B (en) * | 2009-09-24 | 2012-01-18 | 江苏大学 | Cavitation-corrosion-resistant surfacing welding material |
JP5609668B2 (en) * | 2011-01-20 | 2014-10-22 | Jfeスチール株式会社 | Stainless clad steel with excellent seawater pitting resistance |
SG193359A1 (en) * | 2011-03-10 | 2013-10-30 | Nippon Steel & Sumitomo Metal Corp | Duplex stainless steel sheet |
CN102191426B (en) * | 2011-04-14 | 2013-08-28 | 山西太钢不锈钢股份有限公司 | Stainless steel wire for welding and method for smelting steel for wire |
FI125854B (en) * | 2011-11-04 | 2016-03-15 | Outokumpu Oy | Duplex stainless steel |
US9347121B2 (en) * | 2011-12-20 | 2016-05-24 | Ati Properties, Inc. | High strength, corrosion resistant austenitic alloys |
UA111115C2 (en) | 2012-04-02 | 2016-03-25 | Ейкей Стіл Пропертіс, Інк. | cost effective ferritic stainless steel |
WO2015109553A1 (en) * | 2014-01-25 | 2015-07-30 | 吴津宁 | Duplex stainless steel seamless pipe |
BR102014005015A8 (en) * | 2014-02-28 | 2017-12-26 | Villares Metals S/A | martensitic-ferritic stainless steel, manufactured product, process for producing forged or rolled bars or parts of martensitic-ferritic stainless steel and process for producing all seamless martensitic-ferritic stainless steel |
CN104004971B (en) * | 2014-05-09 | 2016-02-03 | 无锡市华尔泰机械制造有限公司 | A kind of alloy material flange and forging process thereof |
MX2019001830A (en) * | 2016-09-02 | 2019-06-06 | Jfe Steel Corp | Duplex stainless steel and method for manufacturing same. |
WO2018114867A1 (en) * | 2016-12-21 | 2018-06-28 | Sandvik Intellectual Property Ab | Use of a duplex stainless steel object |
LT3502293T (en) * | 2017-12-22 | 2020-07-10 | Saipem S.P.A. | Uses of duplex stainless steels |
CN108396257B (en) * | 2018-02-08 | 2020-01-21 | 中国兵器科学研究院宁波分院 | Method for preparing super duplex stainless steel valve for ocean platform by controlled precipitation method |
CN109187322B (en) * | 2018-08-31 | 2021-03-12 | 南京钢铁股份有限公司 | Corrosion resistance evaluation method of low alloy steel for polar region marine environment |
CN109266957A (en) * | 2018-09-18 | 2019-01-25 | 无锡市华尔泰机械制造有限公司 | Modified Z2CND18-12N material flange and its forging method |
CN111020368B (en) * | 2019-10-30 | 2021-07-20 | 鞍钢股份有限公司 | Duplex stainless steel composite steel plate for seawater desalination and manufacturing method thereof |
CN112410675A (en) * | 2020-11-20 | 2021-02-26 | 齐鲁工业大学 | Rare earth double-phase corrosion-resistant cast stainless steel and manufacturing method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0220141A2 (en) * | 1985-09-05 | 1987-04-29 | Santrade Ltd. | High nitrogen containing duplex stainless steel having high corrosion resistance and good structure stability |
EP0455625A1 (en) * | 1990-05-03 | 1991-11-06 | BÖHLER Edelstahl GmbH | High strength corrosion-resistant duplex alloy |
EP0534864A1 (en) * | 1991-09-30 | 1993-03-31 | Sumitomo Metal Industries, Ltd. | Duplex stainless steel having improved corrosion resistance and process for the production thereof |
EP0683241A2 (en) * | 1994-05-21 | 1995-11-22 | Yong Soo Park | Duplex stainless steel with high corrosion resistance |
EP0897018A1 (en) * | 1997-08-13 | 1999-02-17 | BÖHLER Edelstahl GmbH | Duplex stainless steel with high tensile strength and good corrosion properties |
US20010031217A1 (en) * | 2000-03-02 | 2001-10-18 | Orjan Bergstrom | Duplex stainless steel |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1242095A (en) * | 1984-02-07 | 1988-09-20 | Akira Yoshitake | Ferritic-austenitic duplex stainless steel |
JP2500162B2 (en) * | 1991-11-11 | 1996-05-29 | 住友金属工業株式会社 | High strength duplex stainless steel with excellent corrosion resistance |
SE501321C2 (en) * | 1993-06-21 | 1995-01-16 | Sandvik Ab | Ferrite-austenitic stainless steel and use of the steel |
JP3588826B2 (en) * | 1994-09-20 | 2004-11-17 | 住友金属工業株式会社 | Heat treatment method for high nitrogen containing stainless steel |
JP3041050B2 (en) * | 1995-06-05 | 2000-05-15 | ポハング アイアン アンド スチール カンパニー リミテッド | Duplex stainless steel and its manufacturing method |
JPH09209087A (en) * | 1996-02-01 | 1997-08-12 | Sumitomo Metal Mining Co Ltd | Duplex stainless steel |
JPH09279313A (en) * | 1996-04-15 | 1997-10-28 | Sumitomo Metal Ind Ltd | Stainless steel for exhaust gas system of city waste incineration equipment |
CN1068385C (en) * | 1996-10-14 | 2001-07-11 | 冶金工业部钢铁研究总院 | ultra hypoeutectoid, diphasic stainless steel, and prodn. method thereof |
SE9902472L (en) * | 1999-06-29 | 2000-08-07 | Sandvik Ab | Ferrite austenitic steel alloy |
JP3758508B2 (en) * | 2001-02-13 | 2006-03-22 | 住友金属工業株式会社 | Manufacturing method of duplex stainless steel pipe |
SE524952C2 (en) * | 2001-09-02 | 2004-10-26 | Sandvik Ab | Duplex stainless steel alloy |
SE524951C2 (en) * | 2001-09-02 | 2004-10-26 | Sandvik Ab | Use of a duplex stainless steel alloy |
-
2003
- 2003-03-02 SE SE0300574A patent/SE527178C2/en not_active IP Right Cessation
-
2004
- 2004-02-19 US US10/547,572 patent/US20070089810A1/en not_active Abandoned
- 2004-02-19 AU AU2004217572A patent/AU2004217572A1/en not_active Abandoned
- 2004-02-19 EP EP04712794A patent/EP1599612A1/en not_active Withdrawn
- 2004-02-19 EA EA200501409A patent/EA009108B1/en not_active IP Right Cessation
- 2004-02-19 CA CA002519786A patent/CA2519786A1/en not_active Abandoned
- 2004-02-19 CN CNB2004800057521A patent/CN100457953C/en not_active Expired - Fee Related
- 2004-02-19 KR KR1020057016402A patent/KR20060056886A/en not_active Application Discontinuation
- 2004-02-19 JP JP2006507921A patent/JP2006519313A/en active Pending
- 2004-02-19 WO PCT/SE2004/000223 patent/WO2004079027A1/en active Application Filing
-
2005
- 2005-09-02 NO NO20054105A patent/NO20054105L/en not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0220141A2 (en) * | 1985-09-05 | 1987-04-29 | Santrade Ltd. | High nitrogen containing duplex stainless steel having high corrosion resistance and good structure stability |
EP0455625A1 (en) * | 1990-05-03 | 1991-11-06 | BÖHLER Edelstahl GmbH | High strength corrosion-resistant duplex alloy |
EP0534864A1 (en) * | 1991-09-30 | 1993-03-31 | Sumitomo Metal Industries, Ltd. | Duplex stainless steel having improved corrosion resistance and process for the production thereof |
EP0683241A2 (en) * | 1994-05-21 | 1995-11-22 | Yong Soo Park | Duplex stainless steel with high corrosion resistance |
EP0897018A1 (en) * | 1997-08-13 | 1999-02-17 | BÖHLER Edelstahl GmbH | Duplex stainless steel with high tensile strength and good corrosion properties |
US20010031217A1 (en) * | 2000-03-02 | 2001-10-18 | Orjan Bergstrom | Duplex stainless steel |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008054300A1 (en) * | 2006-10-30 | 2008-05-08 | Sandvik Intellectual Property Ab | Duplex stainless steel alloy and use of this alloy |
EA014812B1 (en) * | 2006-10-30 | 2011-02-28 | Сандвик Интеллекчуал Проперти Аб | Duplex stainless steel alloy and use of this alloy |
US9381585B2 (en) | 2010-03-03 | 2016-07-05 | Sandvik Intellectual Property Ab | Method of manufacturing a stainless steel product |
WO2012161661A1 (en) | 2011-05-26 | 2012-11-29 | United Pipelines Asia Pacific Pte Limited | Austenitic stainless steel |
EP2714955A1 (en) * | 2011-05-26 | 2014-04-09 | United Pipelines Limited | Austenitic stainless steel |
EP2714955A4 (en) * | 2011-05-26 | 2015-01-07 | United Pipelines Ltd | Austenitic stainless steel |
AU2012259511B2 (en) * | 2011-05-26 | 2016-12-08 | United Pipelines Asia Pacific Pte Limited | Austenitic stainless steel |
US9803267B2 (en) | 2011-05-26 | 2017-10-31 | Upl, L.L.C. | Austenitic stainless steel |
Also Published As
Publication number | Publication date |
---|---|
EP1599612A1 (en) | 2005-11-30 |
SE0300574D0 (en) | 2003-03-02 |
CN100457953C (en) | 2009-02-04 |
NO20054105D0 (en) | 2005-09-02 |
US20070089810A1 (en) | 2007-04-26 |
SE0300574L (en) | 2004-09-03 |
AU2004217572A1 (en) | 2004-09-16 |
NO20054105L (en) | 2005-09-27 |
CA2519786A1 (en) | 2004-09-16 |
KR20060056886A (en) | 2006-05-25 |
JP2006519313A (en) | 2006-08-24 |
CN1768156A (en) | 2006-05-03 |
EA200501409A1 (en) | 2006-04-28 |
SE527178C2 (en) | 2006-01-17 |
EA009108B1 (en) | 2007-10-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1599612A1 (en) | Duplex stainless steel alloy for use in seawater applications | |
JP4249419B2 (en) | Duplex stainless steel | |
AU2002328002B2 (en) | Duplex steel alloy | |
JPWO2005007915A1 (en) | Martensitic stainless steel | |
AU2002329144B2 (en) | Use of a duplex stainless steel alloy | |
AU2002328002A1 (en) | Duplex steel alloy | |
CA2522352C (en) | Duplex stainless steel alloy and use thereof | |
US20100084121A1 (en) | Plate | |
AU2002329144A1 (en) | Use of a duplex stainless steel alloy | |
EP1129230B1 (en) | New use of a stainless steel in seawater applications | |
JP3470418B2 (en) | High strength austenitic alloy with excellent seawater corrosion resistance and hydrogen sulfide corrosion resistance |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2004217572 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2519786 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004712794 Country of ref document: EP Ref document number: 1733/KOLNP/2005 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20048057521 Country of ref document: CN Ref document number: 2006507921 Country of ref document: JP Ref document number: 1020057016402 Country of ref document: KR |
|
ENP | Entry into the national phase |
Ref document number: 2004217572 Country of ref document: AU Date of ref document: 20040219 Kind code of ref document: A |
|
WWP | Wipo information: published in national office |
Ref document number: 2004217572 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200501409 Country of ref document: EA |
|
WWP | Wipo information: published in national office |
Ref document number: 2004712794 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020057016402 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007089810 Country of ref document: US Ref document number: 10547572 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 10547572 Country of ref document: US |